CN101743116A - 用于芯材料的改进的对接接头 - Google Patents
用于芯材料的改进的对接接头 Download PDFInfo
- Publication number
- CN101743116A CN101743116A CN200880024460A CN200880024460A CN101743116A CN 101743116 A CN101743116 A CN 101743116A CN 200880024460 A CN200880024460 A CN 200880024460A CN 200880024460 A CN200880024460 A CN 200880024460A CN 101743116 A CN101743116 A CN 101743116A
- Authority
- CN
- China
- Prior art keywords
- butt jointing
- fixing butt
- banjo fixing
- methyl
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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Images
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Abstract
本发明的目的是经由沿夹芯复合体结构的厚度方向(z方向)引入增强元件而改进夹芯复合体结构中的对接接头的机械性能。本发明可以用于制备用于航空和航天，以及造船、机动车辆和有轨车辆构造，动力装置构造和运动设备构造中的应用的夹芯复合体。
Description
技术领域
本发明的目的是经由沿夹芯复合体(Kernverbund)结构的厚度方向(z方向)引入增强元件而改进夹芯复合体结构中的对接接头的机械性能。本发明可以用于制备用于航空和航天，以及造船，机动车辆和有轨车辆构造，动力装置构造和运动设备构造中的应用的夹芯复合体。
背景技术
为用于各种应用，将聚甲基丙烯酰亚胺泡沫配备纤维增强的层，以获得具有优异性能的复合材料。这些复合材料尤其用于制备转子叶片(US 5547629)。此外已经描述了与常见的热塑性材料的复合体，例如聚甲基丙烯酰亚胺泡沫材料与聚甲基丙烯酸甲酯的层压(EP 736372)。聚甲基丙烯酰亚胺泡沫的另外应用通过在泡沫内结合入导电性颗粒而成功实现，从而这种泡沫可以用于吸收电磁辐射(DE 38 264 69A1)。也已描述了用于汽车工业的应用(JP 63315229 A2)。其它相关的专利还有DE 3304882 A、GB 1547978 A、DE 2822881、DE 2235028和DE 2114524。
发明内容
目的
在由复合材料构成的构件的制备方面经常遇到的问题是，芯材料(泡沫材料，例如
型泡沫材料，其可在GmbH获得，或还有其它泡沫材料，例如由聚氯乙烯(PVC)或PU构成的泡沫材料)不可以所要求或所希望的尺寸供使用。对于现代大容量客机的方向舵组，例如可能需要大约6m×5m的工件，但是由于制造技术的原因泡沫材料片材仅能以较小的尺寸制备。
除需要以所要求的尺寸提供芯材料之外，还需要将适合于阻止裂纹在泡沫材料内蔓延的增强材料结合到复合构件中。这种功能是尤其重要的，因为裂纹不能从外部辨别出，原因在于覆盖层是不透明的。
在接头，例如对接接头(或称芯连接处)附近，由于刚性突变而在接头位置附近发生应力集中，其可能降低负荷能力。在接头位置，相同或不同的芯材料可以相互重叠地出现。
本发明的目的是开发改进的对接接头。
目的的实现
通过具有产品独立权利要求的所有特征的对接接头达到了上述讨论的目的以及没有单独提及但是对于本领域技术人员可由引入性讨论而毫无困难地推论出的其它目的。本发明膜片的优选的实施方案由引用产品独立权利要求的从属权利要求提供。方法类独立权利要求中保护本发明接头的制备方法。从方法从属权利要求中得到方法的优选的改进方案。通过在夹芯复合体的对接接头附近沿厚度方向引入增强元件，达到了所述目的。在此，不同或相同的芯材料或其它材料可以对接。
本发明的实施方案
可以在具有较低和/或具有较高密度或刚度的芯材料的过渡区中引入增强元件(参见图1)。可以使用的增强元件的实例是碳纤维棒。增强元件另外可以穿透两个覆盖层，以例如改进脱层性能、冲击性能和裂纹蔓延性能，这样的结果是形成更耐受损害的对接接头和整个夹芯结构。可借助常规缝纫或簇绒方法，根据Aztex原理或TFC原理的销连接方法(根据Airbus)，将增强元件引入芯材料或夹芯复合体结构中。
通过将增强元件引入芯材料中，首先可以降低刚度突变，从而可以降低应力集中，其次提高机械性能，例如拉伸性能、压缩性能、抗剪性能和脱层性能。这种有利的影响导致可以提高对接接头的静态和循环强度两者。
增强元件还可以充当止裂器，从而可以防止裂纹可以从对接接头的一侧到另一侧的无阻蔓延。
结果：
●由增强材料所引起的构件的重量增加为大约7％。但是这可以通过使用例如RIMA代替
WF而进一步降低，使得总体上获得重量节约。
●静态抗剪强度提高大约26％，
●提高的循环抗剪强度，
●更长寿命。
对于本发明方法而言相关的芯层包含聚(甲基)丙烯酰亚胺泡沫。
置于括号中的表述意于标明一种任选的特征。例如，(甲基)丙烯酸类是指丙烯酸类、甲基丙烯酸类和两者的混合物。
可从本发明组合物获得的聚(甲基)丙烯酰亚胺泡沫材料包含可以由下式(I)表示的重复单元，
其中
R1和R2是相同或不同的并且可以是氢或甲基，R3可以是氢或含有最多至20个碳原子的烷基或芳基。
结构(I)的单元优选构成聚(甲基)丙烯酰亚胺泡沫材料的多于30重量％，尤其优选多于50重量％，非常尤其优选多于80重量％。
聚(甲基)丙烯酰亚胺硬质泡沫材料的制备是本身已知的，并公开于例如GB专利1078425、GB专利1045229、DE专利1817156(＝US专利3627711)或DE专利2726259(＝US专利4139685)中。
结构式(I)的单元可以例如尤其在加热到150-250℃时从相邻的(甲基)丙烯酸和(甲基)丙烯腈单元通过环化异构化反应而形成(参见DE-C 1817156、DE-C 2726259、EP-B 146892)。通常地，首先经由单体在自由基引发剂存在下，在低温，例如30-60℃下聚合，随后加热到60-120℃而制备前体，该前体然后通过加热到大约180-250℃，经由存在的发泡剂而进行发泡(参见EP-B 356 714)。
为此，例如，可以首先形成共聚物，该共聚物包含(甲基)丙烯酸和(甲基)丙烯腈，优选按1∶3-3∶1的摩尔比。
这些共聚物可以另外包含其它单体单元，所述其它单体单元例如衍生自丙烯酸或甲基丙烯酸的酯，尤其是与含有1-4个碳原子的低级醇，例如甲醇、乙醇、丙醇、异丙醇、正丁醇、异丁醇或叔丁醇的酯，苯乙烯和苯乙烯衍生物，例如α-甲基苯乙烯，马来酸或其酸酐，衣康酸或其酸酐，乙烯基吡咯烷酮、氯乙烯或偏二氯乙烯。不可环化或仅可以很困难地环化的共聚单体的比例应当不超过30重量％，优选20重量％，尤其优选10重量％，基于单体的重量。
作为其它单体，可以按同样已知的方式有利地使用少量交联剂，例如丙烯酸烯丙酯，甲基丙烯酸烯丙酯，乙二醇二丙烯酸酯或乙二醇二甲基丙烯酸酯，或丙烯酸或甲基丙烯酸的多价金属盐，如甲基丙烯酸镁。所述交联剂的用量比例经常为0.005-5重量％，基于可聚合单体的总量。
可以另外使用金属盐添加物，它们通常起减少烟雾的作用。它们尤其包括碱金属或碱土金属或锌、锆或铅的丙烯酸盐或甲基丙烯酸盐。优选(甲基)丙烯酸钠、(甲基)丙烯酸钾、(甲基)丙烯酸锌和(甲基)丙烯酸钙。用量2-5重量份的单体在根据FAR 25.853a的燃烧测试中导致明显地降低烟雾密度。
使用的聚合引发剂是本身通常用于(甲基)丙烯酸酯聚合的那些聚合引发剂，实例是偶氮化合物，如偶氮二异丁腈，以及过氧化物，如过氧化二苯甲酰或过氧化二月桂酰，或其它过氧化物，例如过辛酸叔丁酯或过缩酮，以及非必要的氧化还原引发剂(在此方面参见例如H.Rauch-Puntigam，Th.
Acryl-und Methacrylverbindungen[丙烯酸类和甲基丙烯酸类化合物]，Springer，Heidelberg，1967，或Kirk-Othmer，Encyclopedia of Chemical Technology，第1卷，第286页及其后续页，John Wiley&Sons，纽约，1978)。优选聚合引发剂以用量0.01-0.3重量％使用，基于起始材料。
也可以有利地组合在时间和温度方面具有不同的分解性能的聚合引发剂。例如，同时使用过新戊酸叔丁酯、过苯甲酸叔丁酯和过-2-乙基己酸叔丁酯，或同时使用过苯甲酸叔丁酯、2，2-偶氮双异-2，4-二甲基戊腈、2，2-偶氮二异丁腈和过氧化二叔丁基，是非常适合的。
聚合反应优选通过本体聚合的变化方案进行，实例是所谓的隔槽法，而不限于此。
聚合物的重均分子量Mw优选大于106g/mol，尤其是大于3×106g/mol，但无意由此进行限制。
发泡剂按已知的方式用于将共聚物在转化成含酰亚胺基的聚合物期间发泡，所述发泡剂在150-250℃下经由分解或蒸发形成气相。含有酰胺结构的发泡剂，如尿素，一甲基脲或N，N′-二甲基脲，甲酰胺或一甲基甲酰胺在分解时释放出可以有助于附加形成酰亚胺基团的氨或胺。然而，也可以使用无氮发泡剂，如甲酸，水，或含有3-8个碳原子的一元脂族醇，如1-丙醇、2-丙醇、正1-丁醇、正2-丁醇、异1-丁醇、异2-丁醇、戊醇和/或己醇。发泡剂的用量取决于期望的泡沫材料密度，这里发泡剂在反应批料中的用量通常是大约0.5重量％-15重量％，基于所使用的单体。
另外，前体可包含常规添加剂。它们尤其包括抗静电剂，抗氧化剂，脱模剂，润滑剂，染料，阻燃剂，流动改进剂，填料，光稳定剂和有机磷化合物如亚磷酸酯或膦酸酯，颜料，气候稳定剂和增塑剂。
防止泡沫材料带静电电荷的导电性颗粒是另一类优选的添加剂。它们尤其包括具有尺寸为10nm-10mm的金属颗粒和炭黑颗粒，它们也可以作为纤维存在，如在EP 0356714 A1中所述那样。
可以例如通过以下步骤获得非常尤其优选的可使用的聚甲基丙烯酰亚胺泡沫材料：
1.经由由以下组分组成的组合物的自由基聚合制备聚合物片材：
(a)由20-60重量％甲基丙烯腈，80重量％-40重量％甲基丙烯酸和非必要的最多至20重量％(基于甲基丙烯酸和甲基丙烯腈的总量)的烯属不饱和的其它单官能单体组成的单体混合物，
(b)0.5重量％-15重量％由甲酰胺或一甲基甲酰胺和分子中含3-8个碳原子的一元脂族醇组成的发泡剂混合物，
(c)由以下物质组成的交联剂体系：
(c.1)0.005重量％-5重量％分子中含至少2个双键的能够自由基聚合的烯属不饱和化合物，和
(c.2)1重量％-5重量％溶解在单体混合物中的氧化镁，
(d)引发剂体系，
(e)常规添加剂。
2.在由尺寸50×50cm的两个玻璃板和厚度2.2cm厚的边封形成的隔槽中，在30℃-45℃下使这种混合物聚合多天。然后让该聚合物经历从40℃到130℃的加热调理程序大约20h，以进行聚甲基丙烯酰亚胺最终聚合。随后在200℃-250℃下在数小时期间进行发泡。
此外，可以通过使聚甲基丙烯酸甲酯或其共聚物与伯胺反应获得具有高耐热变形性的聚甲基丙烯酰亚胺，它们同样可以根据本发明使用。对于所述聚合物类似的酰亚胺化反应的大量实例而言代表性地可以提及：US 4246374、EP 216505 A2、EP 860821。在此可以经由使用芳基胺(JP 05222119 A2)或经由使用特殊的共聚单体(EP 561230A2、EP 577002 A1)达到高的耐热变形性。然而，所有这些反应没有得到泡沫，而是得到固体聚合物，其必须在单独的第二个步骤中发泡以获得泡沫。为此的技术也是本领域已知的。
聚(甲基)丙烯酰亚胺硬质泡沫材料也可以在商业上获得，实例是得自
GmbH的
它可以按各种密度和尺寸供应。
聚(甲基)丙烯酰亚胺泡沫的密度优选为20kg/m3-320kg/m3，尤其优选为50kg/m3-110kg/m3。
不希望由此进行限制，芯层的厚度为1mm-200mm，尤其是5mm-100mm，非常尤其优选10mm-70mm。
芯层也可以在内部具有其它层。然而，在本发明的方法中，将聚(甲基)丙烯酰亚胺泡沫与纤维增强的层接合。然而，在本发明方法的特别的实施方案中，使用由聚(甲基)丙烯酰亚胺泡沫组成的芯层。
所使用的纤维增强的层可以包括任何已知的平面成型体，其在制备复合材料所需要的加工参数，例如压力和温度下，是稳定的。具有多层结构的幅材也可以用作纤维增强的层。
例如，它们尤其包括含有聚丙烯、聚酯、聚酰胺、聚氨酯、聚氯乙烯和/或聚(甲基)丙烯酸甲酯的纤维增强的膜片。
纤维增强的层也可以经由包含纤维的已知树脂的固化获得，所述树脂例如是环氧树脂(EP树脂)、甲基丙烯酸酯树脂(MA树脂)、不饱和聚酯树脂(UP树脂)、酚醛树脂、异氰酸酯树脂、双马来酰亚胺树脂和苯基丙烯酸酯树脂(PHA树脂)。
可以使用的纤维增强材料尤其是碳纤维、玻璃纤维、芳族聚酰胺纤维、聚丙烯纤维、聚酯纤维、聚酰胺纤维、聚氨酯纤维、聚(甲基)丙烯酸甲酯纤维、聚氯乙烯纤维和/或金属纤维。
例如，可以优选使用预浸料坯，当中也包括SMC(片状模塑料)，以在芯层上获得纤维增强的层。SMC和预浸料坯是用可固化塑料预浸渍的幅材，通常是玻璃纤维垫或玻璃长丝织造物，或包含碳纤维和/或包含芳族聚酰胺纤维的粗纱，它们可以经热压加工而产生成型件或半成品。可以使用的SMC尤其包括SMC-R(含任意取向纤维的SMC)、SMC-O(含取向纤维的SMC)、SMC-CR(含部分取向的纤维的SMC)、XMC(含网络状纤维增强材料的SMC)和HMC(具有高纤维含量的SMC)。
这些材料是本身已知的并且例如在Ullmann′s Encyclopedia ofIndustrial Chemistry(乌尔曼工业化学大全)，第五版，词目″Fabrication of Polymer Composites″(聚合物复合材料的制造)下进行了描述。
除纤维增强的层之外，还可以经由本发明的方法将由金属构成的层特别牢固地与芯层接合。它们尤其包括由铝构成的薄箔或片材。为了制备复合材料，可以单独地使用或与纤维增强的层一起使用金属层。特别优选的金属层尤其是所谓的铝预浸料坯。
在用有机溶剂处理之后芯层与纤维增强的层或与金属层的接合取决于待施加的层的类型。相应的方法是本身已知的。
例如，包含由聚(甲基)丙烯酰亚胺泡沫构成的芯和纤维增强的层或金属层的复合材料一般可以通过所谓的热压法获得。这些方法是本领域公知的，在此本发明还涵盖特殊的实施方案，例如双带压制、SMC压制和GMT压制。
为了进一步加固复合材料，可以在热压过程中压实芯层。为此，可以在压制工序中使用间隔物，所谓挡块。它们使得更容易调节芯层的期望的压实度，但是不希望对本发明产生任何限制。
为了改进粘附，也可以使用粘合剂，它可以在用有机溶剂处理表面之后涂覆。然而，视纤维增强的层的材料而定，这不是必要的。
例如，为了制备复合材料，可以将SMC层或预浸料坯层以匹配于所述重量的量铺置在模具内的适合尺寸的泡沫材料片材上，并对其施加压制压力。
预浸料坯或SMC开始流动和固化的典型操作条件是大于1N/mm2的压力和60℃-180℃的温度。这些参数也可以阶段梯度形式控制，以避免蓄热。压制持续时间通常是5分钟至6小时，视随纤维增强的层的类型而定。尤其有利的范围是10-120分钟。
此外，上述树脂和纤维增强材料也可以手动涂覆到聚(甲基)丙烯酰亚胺泡沫上。这里，交替地铺置树脂层和纤维幅材。在已经施加纤维增强的树脂层之后，按已知的方式固化树脂。合适的体系可以例如以品名West System从M.u.H.von der Linden GmbH，邮政专用信箱100543，D-46465 Wesel/Rhein获得。
覆盖层的厚度优选为0.1-100mm，优选0.5-50mm，非常尤其优选1-5mm。
附图说明
图1示出了经增强的接头的结构。
图2示出了在未增强的对接接头情况下的通常的力和失效模式。
图3示出了由于对接接头的本发明增强而产生的改进。
本发明增强材料可以用于构造航天器(其中轻质但是稳定的接头特别重要)，以及构造飞机，特别是大容量客机或大容量货运飞机，构造船舶或水翼艇或气垫船，和构造陆上交通工具，例如构造铁路车辆。改进的对接接头的本发明用途的另一种有利的应用是构造风动力装置中的叶片。
Claims (6)
1.夹芯复合体结构中相同或不同芯材料的改进的对接接头，其特征在于将一个或多个增强元件引入所述芯材料的与待改进的对接接头相邻的区域。
2.根据权利要求1的改进的对接接头，其特征在于使用
泡沫材料作为芯材料。
3.根据权利要求1的改进的对接接头，其特征在于使用碳纤维材料部件作为增强元件。
4.根据上述权利要求中任一项的改进的对接接头在航天器、飞机、水上交通工具和陆上交通工具的构造中的用途。
5.根据权利要求1-3中任一项的改进的对接接头在风动力装置的构造中的用途。
6.根据权利要求1-3中任一项的改进的对接接头在运动设备的构造中的用途。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102007033120.9 | 2007-07-13 | ||
| DE102007033120A DE102007033120A1 (de) | 2007-07-13 | 2007-07-13 | Verbesserte Stumpfstoßverbindungen für Kernwerkstoffe |
| PCT/EP2008/054539 WO2009010316A1 (de) | 2007-07-13 | 2008-04-15 | Verbesserte stumpfstossverbindungen für kernwerkstoffe |
Publications (2)
| Publication Number | Publication Date |
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| CN101743116A true CN101743116A (zh) | 2010-06-16 |
| CN101743116B CN101743116B (zh) | 2014-12-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200880024460.0A Expired - Fee Related CN101743116B (zh) | 2007-07-13 | 2008-04-15 | 用于芯材料的改进的对接接头 |
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| Country | Link |
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| US (1) | US20100189954A1 (zh) |
| EP (1) | EP2176056B1 (zh) |
| JP (1) | JP5586459B2 (zh) |
| KR (1) | KR20100032892A (zh) |
| CN (1) | CN101743116B (zh) |
| AU (1) | AU2008277848A1 (zh) |
| BR (1) | BRPI0813721A2 (zh) |
| CA (1) | CA2693889C (zh) |
| DE (1) | DE102007033120A1 (zh) |
| DK (1) | DK2176056T3 (zh) |
| ES (1) | ES2549729T3 (zh) |
| HK (1) | HK1141492A1 (zh) |
| PL (1) | PL2176056T3 (zh) |
| TW (1) | TWI436881B (zh) |
| WO (1) | WO2009010316A1 (zh) |
| ZA (1) | ZA201000234B (zh) |
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| CN102107738A (zh) * | 2009-12-23 | 2011-06-29 | 西北工业大学 | 在轨航天器的柔性自适应对接器 |
| DE102010040286A1 (de) | 2010-08-31 | 2012-03-01 | Evonik Röhm Gmbh | PMI-Schäume mit verbesserten mechanischen Eigenschaften, insbesondere mit erhöhter Reißdehnung |
| CN104619484A (zh) | 2012-07-24 | 2015-05-13 | 赢创工业集团股份有限公司 | Pmi泡沫材料的新成型方法和/或由其制备的复合组件 |
| US11597490B1 (en) | 2021-12-22 | 2023-03-07 | Rapidflight Holdings, Llc | Additive manufactured airframe structure having a plurality of reinforcement elements |
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- 2008-04-15 KR KR1020107000646A patent/KR20100032892A/ko not_active Application Discontinuation
- 2008-04-15 CA CA2693889A patent/CA2693889C/en not_active Expired - Fee Related
- 2008-04-15 CN CN200880024460.0A patent/CN101743116B/zh not_active Expired - Fee Related
- 2008-04-15 DK DK08736231.5T patent/DK2176056T3/en active
- 2008-04-15 BR BRPI0813721-8A2A patent/BRPI0813721A2/pt not_active IP Right Cessation
- 2008-04-15 WO PCT/EP2008/054539 patent/WO2009010316A1/de active Application Filing
- 2008-04-15 US US12/668,713 patent/US20100189954A1/en not_active Abandoned
- 2008-04-15 EP EP08736231.5A patent/EP2176056B1/de not_active Not-in-force
- 2008-04-15 PL PL08736231T patent/PL2176056T3/pl unknown
- 2008-04-15 AU AU2008277848A patent/AU2008277848A1/en not_active Abandoned
- 2008-04-15 JP JP2010515432A patent/JP5586459B2/ja not_active Expired - Fee Related
- 2008-04-15 ES ES08736231.5T patent/ES2549729T3/es active Active
- 2008-07-09 TW TW097125899A patent/TWI436881B/zh not_active IP Right Cessation
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- 2010-01-12 ZA ZA201000234A patent/ZA201000234B/xx unknown
- 2010-08-23 HK HK10108043.8A patent/HK1141492A1/zh not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2176056A1 (de) | 2010-04-21 |
| WO2009010316A9 (de) | 2009-12-17 |
| CA2693889A1 (en) | 2009-01-22 |
| TWI436881B (zh) | 2014-05-11 |
| PL2176056T3 (pl) | 2015-12-31 |
| US20100189954A1 (en) | 2010-07-29 |
| EP2176056B1 (de) | 2015-08-05 |
| DK2176056T3 (en) | 2015-11-02 |
| HK1141492A1 (zh) | 2010-11-12 |
| CA2693889C (en) | 2016-01-05 |
| KR20100032892A (ko) | 2010-03-26 |
| CN101743116B (zh) | 2014-12-24 |
| AU2008277848A1 (en) | 2009-01-22 |
| ES2549729T3 (es) | 2015-11-02 |
| WO2009010316A1 (de) | 2009-01-22 |
| ZA201000234B (en) | 2010-09-29 |
| BRPI0813721A2 (pt) | 2014-12-30 |
| JP2010533216A (ja) | 2010-10-21 |
| DE102007033120A1 (de) | 2009-01-15 |
| JP5586459B2 (ja) | 2014-09-10 |
| TW200918771A (en) | 2009-05-01 |
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